Synthesis of crystalline mordenite-type material

ABSTRACT

This invention relates to a new form of crystalline material identified as mordenite-type, to a new and useful method for synthesizing said crystalline material and to use of said crystalline material prepared in accordance herewith as a catalyst for organic compound, e.g. hydrocarbon compound, conversion.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new and useful method for synthesizing ahighly siliceous form of crystalline material identified asmordenite-type, the new material synthesized, and use of the crystallinematerial synthesized in accordance herewith as a catalyst component fororganic compound, e.g. hydrocarbon compound, conversion.

More particularly, this invention relates to a method for preparing thecrystalline mordenite-type structure whereby synthesis is facilitatedand reproducible and the product exhibits high purity and catalyticutility.

2. Discussion of the Prior Art

Mordenite is a naturally occurring zeolite with an intersecting 12-ringby 8-ring structure. Without an organic directing agent, mordenitetypically crystallizes at silica/alumina mole ratios of about 5 to 10(D. W. Breck, Zeolite Molecular Sieves, 162-163, (1974)). U.S. Pat. Nos.3,996,337; 4,503,023; 4,511,547 and 4,581,216 show synthesis ofmordenite without a directing agent. U.S. Pat. No. 4,377,502 teachessynthesis of mordenite from a reaction mixture comprising a directingagent of triethanolamine, 2-amino-2-ethyl-1,3-propanediol, dioxane ormorpholine. U.S. Pat. No. 4,585,640 shows methyl violet 2B, methyleneblue, methyl viologen or methyl green used as directing agent formordenite synthesis. U.S. Pat. No. 4,376,104 teaches a method forsynthesis of mordenite from a reaction mixture comprising3-dimethylamino-2,2-dimethylpropanol orN,N,2,2-tetramethylpropan-1,3-diamine as directing agent. Piperidine isdisclosed as an organic directing agent for mordenite synthesis by P. A.Jacobs and J. A. Martens, Studies of Surface Science and Catalysis, 33,12 (1987); and 2-amino-pyridine is taught for this purpose in U.S. Pat.No. 4,390,457. Tetra-n-propylammonium salts are taught to be mordenitedirecting agents in U.S. Pat. Nos. 4,707,345 and 4,788,380.

The above disclosures are incorporated herein by reference as tomordenite and its synthesis.

Various organic directing agents are taught for synthesis of variouscrystalline materials. For example, U.S. Pat. No. 4,139,600 teaches amethod for synthesis of zeolite ZSM-5 from a reaction mixturecomprising, as a directing agent, an alkyldiamine. U.S. Pat. No.4,296,083 claims synthesizing zeolites characterized by a ConstraintIndex of 1 to 12 and an alumina/silica mole ratio of not greater than0.083 from a specified reaction mixture containing an organicnitrogen-containing cation provided by an amine identified as beingselected from the group consisting of triethylamine, trimethylamine,tripropylamine, ethylenediamine, propanediamine, butanediamine,pentanediamine, hexanediamine, methylamine, ethylamine, propylamine,butylamine, dimethylamine, diethylamine, dipropylamine, benzylamine,aniline, pyridine, piperidine and pyrrolidine.

U.S. Pat. No. 4,151,189 claims a method for synthesizing zeolites ZSM-5,ZSM-12, ZSM-35 and ZSM-38 containing an organic nitrogen cation from aspecified reaction mixture containing a primary amine having 2 to 9carbon atoms as a directing agent. U.S. Pat. No. 4,341,748 showssynthesis of ZSM-5 structure from reaction mixtures comprising ethanol,ZSM-5 seeds, ethanol and seeds, ethanol and ammonium hydroxide, andethanol, ammonium hydroxide and ZSM-5 seeds. U.S. Pat. No. 4,100,262teaches synthesis of ZSM-5 from a reaction mixture comprising atetraalkylammonium source and a tetraureacobalt (II) complex.

Lok et al. (3 Zeolites, 282-291 (1983)) teach numerous organic compoundswhich act as directing agents for synthesis of various crystallinematerials, such as, for example, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35,ZSM-48, AlPO₄ -5, AlPO₄ -8, AlPO₄ -20 and others. The article does notshow the presently required organic for synthesis of mordenite. Thearticle does show that cyclohexylamine, N-methylcyclohexylamine,dicyclohexylamine and ethyl-n-butylamine may direct synthesis of AlPO₄-5 (U.S. Pat. No. 4,310,440).

U.S. Pat. No. 4,251,499 teaches a method for synthesizing ferrieritefrom a particular reaction mixture containing piperidine oralkyl-substituted piperidine, e.g. 1,2-dimethylpiperidine, as directingagent. U.S. Pat. Nos. 4,016,245 and 4,107,195 show synthesis of ZSM-35from a reaction mixture containing pyrrolidine directing agent.

The zeolitic compositions labeled PSH-3 in U.S. Pat. No. 4,439,409 aresynthesized from reaction mixtures containing hexamethyleneimine asdirecting agent. U.S. Pat. No. 4,954,325 utilizes hexamethyleneimine inanother reaction mixture to direct synthesis of MCM-22. That organic isused in U.S. Pat. No. 4,981,663 for synthesis of yet another crystallinestructure labelled MCM-35.

Other publications teaching various organic directing agents forsynthesis of various crystalline materials include, for example, U.S.Pat. No. 4,592,902, teaching use of an alkyltropinium directing agent,alkyl being of 2 to 5 carbon atoms, for synthesis of ZSM-5; U.S. Pat.No. 4,640,829, teaching use of dibenzyldimethylammonium directing agentfor synthesis of ZSM-50; U.S. Pat. No. 4,637,923, teaching use of (CH₃)₂(C₂ H₅)N⁺ (CH₂)₄ N⁺ (C₂ H₅)(CH₃)₂ directing agent for synthesis ofanother novel zeolite; U.S. Pat. No. 4,585,747, teaching use of bis(N-methylpyridyl) ethylinium directing agent for synthesis of ZSM-48;U.S. Pat. No. 4,585,746, teaching use of bis (N-methylpyridyl)ethylinium directing agent for synthesis of ZSM-12; U.S. Pat. No.4,584,286, teaching use of bis (N-methylpyridyl) ethylinium directingagent for synthesis of ZSM-35; U.S. Pat. No. 4,568,654, teaching use ofcobalticinium, dimethylpiperidinium, trimethylene bis trimethylammoniumor tetramethylpiperazinium directing agents for synthesis of ZSM-51;U.S. Pat. No. 4,559,213, teaching use of DABCO-C₄₋₁₀ -diquat directingagent for synthesis of ZSM-12; U.S. Pat. No. 4,482,531, teachingsynthesis of ZSM-12 with a DABCO-C_(n) -diquat, n being 4, 5, 6 or 10,directing agent; and U.S. Pat. No. 4,539,193, teaching use of bis(dimethylpiperidinium) trimethylene directing agent for synthesis ofZSM-12.

Various diquaternary ammonium compounds have been identified asdirecting agents for a particular assortment of crystalline materials.For instance, U.S. Pat. Nos. 4,490,342 and 4,619,820 show synthesis ofZSM-23 from a reaction mixture containing the organic of U.S. Pat. No.4,531,012, i.e. (CH₃)₃ N⁺ (R)N⁺ (CH₃)₃, where R is a saturated orunsaturated hydrocarbon having 7 carbon atoms. U.S. Pat. No. 4,665,250teaches the use of linear diquaternary ammonium compounds of thestructure (CH₃)₃ N⁺ (CH₂)_(m) N⁺ (CH₃)₃, m being 5, 6, 8, 9 or 10, forsynthesis of ZSM-48. U.S. Pat. No. 4,623,527 teaches numerousdiquaternary ammonium compounds and shows use of (CH₃)₃ N⁺ (CH₂)₇ N⁺(CH₃)₃ directing agent for synthesis of MCM-10.

U.S. Pat. No. 4,632,815 teaches numerous diquaternary ammonium compoundsand shows use of (CH₃)₃ N⁺ (CH₃)₃ to direct synthesis of a Silica-Xstructure-type. U.S. Pat. No. 4,585,639 teaches use of the diquaternary(C₂ H₅)(CH₃)₂ N⁺ (CH₂)_(4or6) N⁺ (CH₃)₂ (C₂ H₅) as directing agent forsynthesis of ZSM-12. Synthesis of ZSM-5 is directed by the diquaternary(alkyl)₃ N⁺ (CH₂)₆ N⁺ (alkyl)₃, alkyl being propyl or butyl, in U.S.Pat. No. 4,585,638.

EPA 42,226 and U.S. Pat. No. 4,537,754 teach existence of numerousdiquaternary ammonium compounds, but show use of (CH₃)₃ N⁺ (CH₂)₆ N⁺(CH₃)₃ as directing agent for synthesis of EU-1. EPA 51,318 teaches useof the same diquaternary for synthesis of TPZ-3. It is noted that EU-1,TPZ-3 and ZSM-50 (synthesized with dibenzyldimethylammonium directingagent) have the same structure.

Applicants know of no prior art method for preparing a highly siliceouscrystalline mordenite structure utilizing the present method.

SUMMARY OF THE INVENTION

An economical and reproducible method for preparing a crystallinematerial identified as synthetic mordenite exhibiting high purity,catalytic activity and other valuable properties is provided. The methodcomprises forming a reaction mixture hydrogel containing sources ofalkali or alkaline earth metal (M) cations; an oxide of trivalentelement (X), e.g. aluminum, boron, iron, gallium, indium and mixturesthereof; an oxide of tetravalent element (Y), e.g. silicon, germanium,tin and mixtures thereof; a directing agent (R) of1,8-diamino-p-menthane; and water, said reaction mixture having acomposition in terms of mole ratios, within the following ranges:

    ______________________________________                                        Reactants    Useful            Preferred                                      ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                  1 to    70     10 to    30                                       H.sub.2 O/YO.sub.2                                                                         10 to   100    15 to    50                                       OH.sup.- /YO.sub.2                                                                         0 to    0.25   0 to     0.1                                      M/YO.sub.2   0 to    2.0    0.10 to  1.0                                      R/YO.sub.2   0.10 to 2.0    0.16 to  1.0                                      ______________________________________                                    

The method further comprises maintaining the reaction mixture untilcrystals of mordenite structure are formed. Reaction conditions requiredconsist of heating the foregoing reaction mixture to a temperature offrom about 100° C. to about 200° C. for a period of time of from about10 hours to about 10 days. A more preferred temperature range is fromabout 130° C. to about 180° C. with the amount of time at a temperaturein such range being from about 2 days to about 8 days.

The solid product comprising mordenite crystals is recovered from thereaction medium, as by cooling the whole to room temperature, filteringand water washing.

EMBODIMENTS

The particular effectiveness of the presently required organic directingagent, i.e. 1,8-diamino-p-menthane, when compared with other directingagents, such as those identified above, for the present synthesis isbelieved due to its ability to function as a template in the nucleationand growth of mordenite crystals from the above low YO₂, e.g. SiO₂, lowalkalinity, e.g. low OH⁻ /YO₂, reaction mixture. This is true eventhough no predigestion of the gel is required prior to crystallization.This different organic agent functions in this fashion in the reactionmixture having the above described composition and under the abovedescribed conditions of temperature and time. The reaction mixturerequired for this invention is X-rich, e.g. aluminum-rich, with a YO₂/X₂ O₃ molar ratio of from about 1/1 to about 70/1, preferably fromabout 10/1 to about 30/1.

It should be noted that the ratio of components of the reaction mixturerequired herein are critical to achieve maximum effectiveness. Forinstance, if the YO₂ /X₂ O₃ ratio is above about 30, especially aboveabout 70, something other than mordenite will begin to form as impurity.In general, with higher YO₂ /X₂ O₃ ratios in the reaction mixture,crystallization of synthetic ZSM-5 increases and mordenite decreases.When the YO₂ /X₂ O₃ ratio is greater than about 70/1, ZSM-5 becomes theprimary product. Further, at these lower YO₂ /X₂ O₃ molar ratios, i.e.less than about 30/1, the R/YO₂ mole ratio minimum for most successfulmordenite synthesis is about 0.16/1. When this ratio drops below about0.16 at the YO₂ /X₂ O₃ ratios of 30 or less, mixtures of mordenite andZSM-5 comprise the product. Still further, for most effective synthesisof mordenite by this method, the reaction temperature should not exceedabout 180° C.

The synthesis of the present invention is facilitated when the reactionmixture comprises seed crystals, such as those having the structure ofmordenite. The use of at least 0.01%, preferably about 0.10%, and evenmore preferably about 1% seed crystals (based on total weight) ofcrystalline material will be useful.

The reaction mixture composition for the synthesis of mordenite-typecrystals hereby can be prepared utilizing materials which can supply theappropriate oxide. The useful sources of X₂ O₃, e.g. aluminum oxide,iron oxide and/or boron oxide, include, as non-limiting examples, anyknown form of such oxide, e.g. aluminum oxide or hydroxide, organic orinorganic salt or compound, e.g. alumina, aluminates and borates. Theuseful sources of YO₂, e.g. silicon oxide, include, as non-limitingexamples, known forms of such oxide, e.g. silicic acid or silicondioxide, alkoxy- or other compounds of silicon, including silica gel andsilica hydrosol.

It will be understood that each oxide component utilized in the reactionmixture for this synthesis can be supplied by one or more essentialreactants and they can be mixed together in any order. For example, anyoxide can be supplied by an aqueous solution. The reaction mixture canbe prepared either batchwise or continuously. Crystal size andcrystallization time for the product composition comprising themordenite crystals will vary with the exact nature of the reactionmixture employed within the above limitations.

The 1,8-diamino-p-menthane directing agent for use herein has a formulaC₁₀ H₂₂ N₂, and may be structurally represented as follows: ##STR1##

The mordenite crystal composition prepared hereby has a characteristicX-ray diffraction pattern, including values substantially as set forthin Table 1, hereinafter.

                  TABLE 1                                                         ______________________________________                                        Interplanar d-Spacing, (A)                                                                       Relative Intensity (I/I.sub.o)                             ______________________________________                                        13.59     ± 0.10    m                                                      10.23     ± 0.10    w-m                                                    9.05      ± 0.10    s-vs                                                   6.57      ± 0.10    s                                                      6.39      ± 0.06    w                                                      6.06      ± 0.05    w                                                      5.80      ± 0.03    w-m                                                    4.50      ± 0.05    m-s                                                    4.25      ± 0.15    w                                                      4.00      ± 0.05    s-vs                                                   3.83      ± 0.02    w-m                                                    3.76      ± 0.02    w                                                      3.47      ± 0.04    vs                                                     3.41      ± 0.03    s} twin peaks                                          3.38      ± 0.03    s} not fully resolved                                  3.22      ± 0.03    m-s                                                    2.89      ± 0.02    w-m                                                    ______________________________________                                    

These X-ray diffraction data were collected with a Rigaku diffractionsystem, equipped with a graphite diffracted beam monochromator andscintillation counter, using copper K-alpha radiation. The diffractiondata were recorded by step-scanning at 0.02 degrees of two-theta, wheretheta is the Bragg angle, and a counting time of 1 second for each step.The interplanar spacings, d's , were calculated in Angstrom units (A),and the relative intensities of the lines I/I_(o), where I_(o) isone-hundredth of the intensity of the strongest line, above background,were derived with the use of a profile fitting routine (or secondderivative algorithm). The intensities are uncorrected for Lorentz andpolarization effects. The relative intensities are given in terms of thesymbols vs = very strong (75-100), s = strong (50-74), m = medium(25-49) and w = weak (0-24). It should be understood that diffractiondata listed for this sample as single lines may consist of multipleoverlapping lines which under certain conditions, such as differences incrystallite sizes or very high experimental resolution orcrystallographic change, may appear as resolved or partially resolvedlines. Typically, crystallographic changes can include minor changes inunit cell parameters and/or a change in crystal symmetry, without achange in topology of the structure. These minor effects, includingchanges in relative intensities, can also occur as a result ofdifferences in cation content, framework composition, nature and degreeof pore filling, and thermal and/or hydrothermal history.

The crystalline mordenite prepared hereby has a composition involvingthe molar relationship:

    X.sub.2 O.sub.3 :(y)YO.sub.2

wherein X is a trivalent element, such as aluminum, boron, iron, indiumand/or gallium, preferably aluminum; Y is a tetravalent element, such assilicon, tin and/or germanium, preferably silicon; and y is from about 1to about 70, usually from about 10 to about 50, more usually from about20 to about 30. In the as-synthesized form, the crystalline material hasa formula, on an anhydrous basis and in terms of moles of oxides per ymoles of YO₂, as follows:

    (0.1 to 1.1)M.sub.2 O:(0.1 to 1.1)R:X.sub.2 O.sub.3 :(y)YO.sub.2

wherein M and R are as defined above. The M and R components areassociated with the material as a result of their presence duringcrystallization, and are easily removed by post-crystallization methodshereinafter more particularly described.

Synthetic mordenite-type crystals prepared in accordance herewith can beused either in the as-synthesized form, the hydrogen form or anotherunivalent or multivalent cationic form. It can also be used in intimatecombination with a hydrogenating component such as tungsten, vanadium,molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noblemetal such as platinum or palladium where a hydrogenationdehydrogenationfunction is to be performed. Such components can be exchanged into thecomposition, impregnated therein or physically intimately admixedtherewith. Such components can be impregnated in or on to the mordenitesuch as, for example, by, in the case of platinum, treating the materialwith a platinum metal-containing ion. Suitable platinum compounds forthis purpose include chloroplatinic acid, platinous chloride and variouscompounds containing the platinum amine complex. Combinations of metalsand methods for their introduction can also be used.

Synthetic mordenite crystals, when employed either as an adsorbent or asa catalyst in a hydrocarbon conversion process, should be dehydrated atleast partially. This can be done by heating to a temperature in therange of from about 65° C. to about 315° C. in an inert atmosphere, suchas air, nitrogen, etc. and at atmospheric or subatmospheric pressuresfor between 1 and 48 hours. Dehydration can be performed at lowertemperature merely by placing the zeolite in a vacuum, but a longer timeis required to obtain a particular degree of dehydration. The thermaldecomposition product of the newly synthesized mordenite can be preparedby heating same at a temperature of from about 200° C. to about 550° C.for from 1 hour to about 48 hours.

The original cations, e.g. alkali or alkaline earth metal, of theas-synthesized material can be replaced in accordance with techniqueswell known in the art, at least in part, by ion exchange with othercations. Preferred replacing cations include metal ions, hydrogen ions,hydrogen precursor, e.g. ammonium, ions and mixtures thereof.Particularly preferred cations are those which render the materialcatalytically active, especially for certain hydrocarbon conversionreactions. These include hydrogen, rare earth metals and metals ofGroups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Tableof the Elements, especially gallium, indium and tin.

Typical ion exchange technique would be to contact the syntheticmordenite material with a salt of the desired replacing cation orcations. Examples of such salts include the halides, e.g. chlorides,nitrates and sulfates.

Representative ion exchange techniques are disclosed in a wide varietyof patents including U.S. Pat. Nos. 3,140,249; 3,140,251; and 3,140,253.

Following contact with the salt solution of the desired replacingcation, the mordenite is then preferably washed with water and dried ata temperature ranging from 65° C. to about 315° C. and thereafter may becalcined in air or other inert gas at temperatures ranging from about200° C. to about 550° C. for periods of time ranging from 1 to 48 hoursor more to produce a catalytically-active thermal decomposition productthereof.

The crystalline mordenite prepared by the instant invention is formed ina wide variety of particle sizes. Generally speaking, the particles canbe in the form of a powder, a granule, or a molded product, such asextrudate having particle size sufficient to pass through a 2 mesh(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In caseswhere the catalyst is molded, such as by extrusion, the crystallinematerial can be extruded before drying or dried or partially dried andthen extruded.

In the case of many catalysts, it is desired to incorporate the crystalshereby prepared with another material resistant to the temperatures andother conditions employed in certain organic conversion processes. Suchmatrix materials include active and inactive materials and synthetic ornaturally occurring zeolites as well as inorganic materials such asclays, silica and/or metal oxides, e.g. alumina, titania and/orzirconia. The latter may be either naturally occurring or in the form ofgelatinous precipitates, sols or gels including mixtures of silica andmetal oxides. Use of a material in conjunction with the mordenite, i.e.combined therewith, which is active, may enhance the conversion and/orselectivity of the catalyst in certain organic conversion processes.Inactive materials suitably serve as diluents to control the amount ofconversion in a given process so that products can be obtainedeconomically and orderly without employing other means for controllingthe rate or reaction. Frequently, crystalline catalytic materials havebeen incorporated into naturally occurring clays, e.g. bentonite andkaolin. These materials, i.e. clays, oxides, etc., function, in part, asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in a petroleum refinery the catalyst isoften subjected to rough handling, which tends to break the catalystdown into powder-like materials which cause problems in processing.

Naturally occurring clays which can be composited with the herebysynthesized crystalline material include the montmorillonite and kaolinfamilies which include the subbentonites, and the kaolins commonly knownas Dixie, McNamee, Georgia and Florida clays, or others in which themain mineral constituent is halloysite, kaolinite, dickite, nacrite oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, acid treatment or chemicalmodification.

In addition to the foregoing materials, the present crystals can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania, as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia. The matrix can be in the form of a cogel.A mixture of these components could also be used.

The relative proportions of finely divided crystalline material andmatrix vary widely with the crystalline material content ranging fromabout 1 to about 90 percent by weight, and more usually in the range ofabout 2 to about 50 percent by weight of the composite.

Employing a catalytically active form of the catalyst of this inventionwhich may contain additional hydrogenation components, reforming stockscan be reformed employing a temperature between about 370° C. and about540° C. The pressure can be between about 100 psig and about 1000 psig,but it is preferably between about 200 psig and about 700 psig. Theliquid hourly space velocity is generally between about 0.1 and about 10hr⁻¹, preferably between about 0.5 and about 4 hr⁻¹, and the hydrogen tohydrocarbon mole ratio is generally between about 1 and about 20,preferably between about 4 and about 12 .

The catalyst can also be used for hydroisomerization of normalparaffins, when provided with a hydrogenation component, e.g. platinum.Hydroisomerization is carried out at a temperature between about 90° C.and 375° C., preferably about 145° C. to about 290° C., with a liquidhourly space velocity between about 0.01 and about 2 hr⁻¹, preferablybetween about 0.25 and about 0.50 hr⁻¹, employing hydrogen such that thehydrogen to hydrocarbon mole ratio is between about 1:1 and about 5:1.

The catalyst can also be used for reducing the pour point of gas oils.This reaction may be conducted at a liquid hourly space velocity betweenabout 10 and about 30 hr⁻¹ and at a temperature between about 400° C.and about 540° C.

Other reactions which can be accomplished employing the catalyst of thisinvention containing a metal, e.g. platinum, includehydrogenation-dehydrogenation reactions and desulfurization reactions.

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following examples are presented. In theexamples, whenever adsorption data are set forth for comparison ofsorptive capacities, they are determined as follows:

A weighed sample of the calcined adsorbant is contacted with the desiredpure adsorbate vapor in an adsorption chamber, evacuated to 1 mm andcontacted with either 5 mm or 12 mm Hg of water vapor, 20 mm Hg ofn-hexane or cyclohexane vapor, or 100mm Hg of n-butane or neopentanevapor, pressures less than the vapor-liquid equilibrium pressure of therespective adsorbate at room temperature. The pressure is kept constant(within about ±0.5 mm) by addition of absorbate vapor controlled by amanostat during the adsorption period, which does not exceed about 8hours. As adsorbate is adsorbed by the sorbant material, the decrease inpressure causes the manostat to open a valve which admits more adsorbatevapor to the chamber to restore the above control pressures. Sorption iscomplete when the pressure change is not sufficient to activate themanostat. The increase in weight is calculated as the adsorptioncapacity of the sample in g/100 g of calcined adsorbant.

When Alpha Value is examined, it is noted that the Alpha Value is anapproximate indication of the catalytic cracking activity of thecatalyst compared to a standard catalyst and it gives the relative rateconstant (rate of normal hexane conversion per volume of catalyst perunit time). It is based on the activity of silica-alumina crackingcatalyst taken as an Alpha of 1 (Rate Constant=0.016 sec⁻¹). The AlphaTest is described in U.S. Pat. No. 3,354,078; in the Journal ofCatalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol 61, p.395 (1980), each incorporated herein by reference as to thatdescription. The experimental conditions of the test used herein includea constant temperature of 538° C. and a variable flow rate as describedin detail in the Journal of Catalysis, Vol. 61, p. 395.

EXAMPLE 1

To water (47.21 g) was added sodium aluminate (1.45 g, technical grade,74% solids), and sodium hydroxide (0.535 g). This mixture was stirredbriefly to complete dissolution, then 1,8-diamino-p-menthane (7.508 g)was added. To this solution was added silica (Ultrasil, 9.137 g), andthe resulting gel was transferred to a teflon liner, placed in anautoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 345 rpm) for 1 week. The final hydrogel is described bythe mole ratios as follows:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3                                                           21.27                                                                 OH.sup.- /SiO.sub.2                                                                   0                                                                     R/SiO.sub.2                                                                           0.31                                                                  H.sub.2 O/SiO.sub.2                                                                   19.03                                                                 Na.sup.+ /SiO.sub.2                                                                   0.2                                                            ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (8.687 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be mordenite,and is shown in Table 2.

A portion of the as-synthesized product of this example was calcined at538° C. for 10 hours. Table 3 shows the X-ray diffraction pattern ofthis calcined mordenite material.

                  TABLE 2                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        13.60           6.50     40.83                                                10.26           8.62     17.82                                                9.08            9.74     85.49                                                6.58            13.46    68.57                                                6.40            13.84    17.99                                                6.21            14.26    6.43                                                 6.06            14.62    14.95                                                5.81            15.26    32.58                                                4.87            18.20    5.84                                                 4.52            19.62    63.84                                                4.45            19.96    7.73                                                 4.11            21.44    10.03                                                3.99            22.28    92.29                                                3.83            23.22    24.49                                                3.76            23.68    13.96                                                3.62            24.58    6.45                                                 3.47            25.68    100.00                                               3.39            26.32    57.10                                                3.22            27.66    62.00                                                3.16            28.28    7.68                                                 3.15            28.36    7.68                                                 3.10            28.82    9.08                                                 2.93            30.48    10.55                                                2.89            30.96    24.30                                                2.70            33.20    6.66                                                 ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        13.64           6.48     35.18                                                10.23           8.64     24.94                                                9.10            9.72     100.00                                               6.58            13.46    72.44                                                6.39            13.86    21.64                                                6.18            14.34    7.39                                                 6.06            14.62    16.88                                                5.81            15.26    29.27                                                5.11            17.36    7.26                                                 5.03            17.62    7.21                                                 4.52            19.64    49.57                                                4.15            21.42    6.75                                                 3.99            22.30    87.28                                                3.83            23.24    22.85                                                3.75            23.72    14.89                                                3.63            24.52    7.59                                                 3.57            24.94    6.85                                                 3.47            25.68    93.85                                                3.38            26.34    62.04                                                3.22            27.68    63.59                                                3.15            28.34    9.88                                                 3.10            28.82    9.60                                                 2.93            30.48    11.15                                                2.89            30.94    25.77                                                2.70            33.16    6.48                                                 2.69            33.32    6.52                                                 ______________________________________                                    

The hydrogen-ion form of the calcined product of this example proves tohave an Alpha Value of 430, and the following equilibrium adsorptioncapacities in grams/100 grams:

    ______________________________________                                               H.sub.2 O                                                                             13.6                                                                  Neopentane                                                                            4.6                                                                   n-Butane                                                                              5.3                                                            ______________________________________                                    

EXAMPLE 2

To water (47.227 g) was added sodium aluminate (1.44 g, technical grade,74% solids) and sodium hydroxide (0.541 g). This mixture was stirredbriefly to complete dissolution, then 1,8-diamino-p-methane (7.509 g)was added. To this solution was added silica (Ultrasil, 9.116 g), andthe resulting gel was transferred to a teflon liner, placed in anautoclave, pressurized (100 psig), sealed, then heated (175° C.) withstirring (.sup.˜ 355 rpm) for 3 days. The final hydrogel had thefollowing composition in terms of mole ratios:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3                                                           21.41                                                                 OH.sup.- /SiO.sub.2                                                                   0                                                                     R/SiO.sub.2                                                                           0.31                                                                  H.sub.2 O/SiO.sub.2                                                                   19.08                                                                 Na.sup.+ /SiO.sub.2                                                                   0.20                                                           ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (9.007 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be syntheticmordenite as shown in Table 4.

A portion of the as-synthesized product of this example was calcined at538° C. for 10 hours. Table 5 shows the X-ray diffraction pattern ofthis calcined mordenite material.

                  TABLE 4                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        13.64           6.48     39.81                                                10.28           8.60     17.89                                                9.10            9.72     68.71                                                6.58            13.46    56.39                                                6.40            13.84    19.95                                                6.24            14.20    5.20                                                 6.06            14.62    13.30                                                5.81            15.26    26.74                                                5.04            17.58    4.87                                                 4.87            18.20    5.62                                                 4.52            19.62    58.92                                                4.27            20.80    6.14                                                 4.23            21.00    6.00                                                 4.15            22.40    10.82                                                4.10            21.70    7.96                                                 3.99            22.26    100.00                                               3.83            23.20    22.34                                                3.75            23.70    12.22                                                3.62            24.60    5.57                                                 3.57            24.92    4.73                                                 3.53            25.26    10.21                                                3.47            25.66    83.04                                                3.39            26.32    58.41                                                3.28            27.16    8.34                                                 3.22            27.66    49.70                                                3.15            28.34    6.84                                                 3.10            28.76    7.82                                                 2.94            30.42    9.70                                                 2.89            30.92    20.66                                                2.71            33.10    5.53                                                 2.70            33.22    6.56                                                 2.57            34.97    4.87                                                 ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        13.64           6.48     32.69                                                10.26           8.62     24.03                                                9.10            9.72     79.00                                                6.58            13.46    61.57                                                6.39            13.86    24.63                                                6.06            14.62    15.25                                                5.81            15.26    24.71                                                5.11            17.34    5.55                                                 5.03            17.62    6.17                                                 4.86            18.26    4.97                                                 4.52            19.62    47.19                                                4.27            20.80    6.03                                                 4.22            21.04    6.20                                                 4.14            21.44    7.51                                                 4.10            21.68    7.92                                                 3.99            22.30    100.00                                               3.83            23.22    22.65                                                3.75            23.70    12.74                                                3.62            24.56    6.49                                                 3.57            24.94    5.09                                                 3.47            25.68    83.32                                                3.38            26.34    67.17                                                3.29            27.14    8.55                                                 3.22            27.66    54.82                                                3.15            28.30    8.26                                                 3.10            28.82    8.89                                                 2.94            30.44    10.89                                                2.89            30.98    23.55                                                2.69            33.34    5.89                                                 2.63            34.12    4.63                                                 ______________________________________                                    

The hydrogen-ion form of the calcined product of this example proves tohave an Alpha Value of about 430, and the following equilibriumadsorption capacities in grams/100 grams:

    ______________________________________                                               H.sub.2 O                                                                             13.6                                                                  Neopentane                                                                            4.6                                                                   n-Butane                                                                              5.3                                                            ______________________________________                                    

EXAMPLE 3

To water (47.222 g) was added sodium aluminate (0.28 g, technical grade,74% solids) and sodium hydroxide (0.543 g). This mixture was stirredbriefly to complete dissolution, then 7.558 g of 1,8-diamino-p-menthanewas added. To this solution was added silica (Ultrasil, 9.146 g), andthe resulting gel was transferred to a teflon liner, placed in anautoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 360 rpm) for 1 week. The final hydrogel had thefollowing composition in terms of mole ratios:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3                                                           103.39                                                                OH.sup.- /SiO.sub.2                                                                   0.08                                                                  R/SiO.sub.2                                                                           0.32                                                                  H.sub.2 O/SiO.sub.2                                                                   18.90                                                                 Na.sup.+ /SiO.sub.2                                                                   0.12                                                           ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (8.811 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be syntheticZSM-5 with amorphous impurity, instead of mordenite, as shown in Table6.

A portion of the as-synthesized product of this example was calcined at538° C. for 10 hours. Table 7 shows the X-ray diffraction pattern ofthis calcined product material.

                  TABLE 6                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        20.27           4.36     54.04                                                11.22           7.88     71.60                                                10.03           8.82     47.84                                                7.49            11.82    14.95                                                7.34            12.06    10.59                                                7.09            12.48    10.72                                                6.74            13.14    13.52                                                6.40            13.84    16.16                                                6.03            14.70    18.01                                                5.73            15.46    14.83                                                5.60            15.82    17.38                                                5.39            16.44    9.63                                                 5.16            17.20    11.84                                                5.00            17.72    16.75                                                4.85            18.30    9.52                                                 4.63            19.16    14.34                                                4.46            19.90    9.81                                                 4.39            20.24    18.49                                                4.28            20.74    17.34                                                4.19            21.22    9.27                                                 4.11            21.62    12.22                                                4.02            22.12    13.66                                                3.87            22.98    100.00                                               3.84            23.18    71.27                                                3.74            23.82    52.71                                                3.67            24.28    34.30                                                3.62            24.62    17.00                                                3.56            24.98    16.70                                                3.45            25.80    76.51                                                3.37            26.44    32.00                                                3.35            26.58    31.73                                                3.33            26.74    31.83                                                3.26            27.38    25.76                                                3.23            27.62    30.18                                                3.06            29.16    16.89                                                3.00            29.76    18.47                                                2.99            29.92    19.95                                                2.95            30.26    14.41                                                ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        17.89           4.94     31.42                                                11.25           7.86     78.05                                                10.10           8.76     54.45                                                8.69            10.18    16.96                                                7.39            11.98    17.16                                                6.74            13.14    17.64                                                6.38            13.88    23.79                                                6.04            14.66    27.45                                                5.72            15.48    21.30                                                5.60            15.82    22.69                                                5.39            16.44    12.54                                                5.17            17.16    14.52                                                4.99            17.76    18.66                                                4.91            18.08    13.27                                                4.80            18.48    12.45                                                4.63            19.16    18.80                                                4.38            20.28    24.19                                                4.28            20.74    24.11                                                4.10            21.66    21.41                                                4.02            22.12    20.87                                                3.87            23.00    100.00                                               3.83            23.22    76.23                                                3.73            23.86    58.16                                                3.66            24.34    38.75                                                3.41            26.12    93.31                                                3.26            27.40    19.04                                                3.19            27.98    15.80                                                3.15            28.34    15.36                                                3.06            29.18    19.80                                                3.00            29.80    21.70                                                2.86            31.22    12.01                                                2.74            32.70    11.64                                                ______________________________________                                    

The hydrogen-ion form of the calcined product of this example proves tohave an Alpha Value of 100, and the following equilibrium adsorptioncapacities in grams/100 grams:

    ______________________________________                                               H.sub.2 O                                                                              7.2                                                                  Cyclohexane                                                                            7.8                                                                  n-Hexane 11.1                                                          ______________________________________                                    

EXAMPLE 4

To water (47.216 g) was added sodium aluminate (1.45 g, technical grade,74% solids) and sodium hydroxide (0.544 g). This mixture was stirredbriefly to complete dissolution, then 1,8-diamino-p-menthane (3.774 g)was added. To this solution was added silica (Ultrasil, 9.148 g), andthe resulting gel was transferred to a teflon liner, placed in anautoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 360 rpm) for 1 week. The final hydrogel is described bythe moles ratios as follows:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3                                                           21.27                                                                 OH.sup.- /SiO.sub.2                                                                   0                                                                     R/SiO.sub.2                                                                           0.16                                                                  H.sub.2 O/SiO.sub.2                                                                   19.01                                                                 Na.sup.+ /SiO.sub.2                                                                   0.20                                                           ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (8.313 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be a mixtureof ZSM-5 and mordenite, as shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        13.43           6.58     28.25                                                11.14           7.94     13.62                                                10.09           8.76     14.49                                                9.41            9.40     70.37                                                9.01            9.82     69.90                                                7.01            12.62    19.11                                                6.90            12.82    18.69                                                6.54            13.54    55.19                                                6.35            13.94    11.54                                                6.02            14.72    11.30                                                5.76            15.38    28.18                                                5.64            15.70    8.87                                                 5.01            17.70    5.81                                                 4.85            18.30    5.51                                                 4.72            18.78    4.78                                                 4.50            19.72    39.87                                                4.36            20.36    4.41                                                 4.26            20.86    4.51                                                 4.21            21.10    4.64                                                 4.12            22.58    8.05                                                 3.97            22.38    81.83                                                3.92            22.68    23.41                                                3.82            23.28    35.05                                                3.76            23.64    34.03                                                3.72            23.92    19.18                                                3.65            24.38    21.54                                                3.52            25.28    45.19                                                3.46            25.78    100.00                                               3.37            26.42    43.24                                                3.30            27.00    13.98                                                3.21            27.80    46.61                                                3.12            28.60    18.25                                                3.04            29.40    14.72                                                2.99            29.86    5.09                                                 2.98            30.00    5.81                                                 2.94            30.36    9.69                                                 2.92            30.60    10.17                                                2.88            31.04    22.05                                                2.70            33.18    8.38                                                 2.64            33.96    6.19                                                 2.62            34.22    4.63                                                 2.58            34.84    5.75                                                 ______________________________________                                    

EXAMPLE 5

To water (47.232 g) was added sodium aluminate (0.29 g, technical grade,74% solids) and sodium hydroxide (0.52 g). This mixture was stirredbriefly to complete dissolution, then 1,8-diamino-p-menthane (7.542 g)was added. To this solution was added silica (Ultrasil, 9.129 g), andthe resulting gel was transferred to a teflon liner, placed in anautoclave, pressurized (100 psig), sealed, then heated (175° C.) withstirring (.sup.˜ 360 rpm) for 3 days. The final hydrogel is described bythe moles ratios as follows:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3                                                                 102.87                                                          OH.sup.- /SiO.sub.2                                                                         0.07                                                            R/SiO.sub.2   0.32                                                            H.sub.2 O/SiO.sub.2                                                                         18.94                                                           Na.sup.+ /SiO.sub.2                                                                         0.12                                                     ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (8.388 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be devoid ofany mordenite, but to comprise a layered material and amorphousmaterial, and is shown in Table 9.

                  TABLE 9                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        20.45           4.32     78.40                                                13.68           6.46     18.28                                                11.22           7.88     19.32                                                10.07           8.78     26.65                                                9.04            9.78     20.05                                                7.34            12.06    14.42                                                6.59            13.44    21.54                                                6.08            14.56    13.75                                                5.79            15.30    14.27                                                4.98            17.80    23.09                                                4.53            19.60    24.09                                                4.16            21.38    26.50                                                3.99            22.28    34.83                                                3.87            22.98    33.53                                                3.68            24.16    32.22                                                3.46            25.74    100.00                                               3.22            27.66    48.40                                                2.94            30.38    17.07                                                ______________________________________                                    

EXAMPLE 6

To water (47.212 g) was added sodium aluminate (1.43 g, technical grade,74% solids) and sodium hydroxide (0.525 g). This mixture was stirredbriefly to complete dissolution, then 1,8-diamino-p-menthane (3.753 g)was added. To this solution was added silica (Ultrasil, 9.127 g), andthe resulting gel was transferred to a teflon liner, placed in anautoclave, pressurized (100 psig), sealed, then heated (95° C.) withstirring (.sup.˜ 340 rpm) for 1 week. The final hydrogel is described bythe moles ratios as follows:

    ______________________________________                                               SiO.sub.2 Al.sub.2 O.sub.3                                                            21.54                                                                 OH.sup.- /SiO.sub.2                                                                   0                                                                     R/SiO.sub.2                                                                           0.16                                                                  H.sub.2 O/SiO.sub.2                                                                   19.05                                                                 Na.sup.+ /SiO.sub.2                                                                   0.19                                                           ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (9.398 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be amorphous.

EXAMPLE 7

To water (47.218 g) was added sodium aluminate (0.29 g, technical grade,74% solids) and sodium hydroxide (0.535 g). This mixture was stirredbriefly to complete dissolution, then 1,8-diamino-p-menthane (7.528 g)was added. To this solution was added silica (Ultrasil, 9.121 g), andthe resulting gel was transferred to a teflon liner, placed in anautoclave, pressurized (100 psig), sealed, then heated (175° C.) withstirring (.sup.˜ 350 rpm) for 5 days. The final hydrogel is described bythe moles ratios as follows:

    ______________________________________                                               SiO.sub.2 Al.sub.2 O.sub.3                                                            101.77                                                                OH.sup.- /SiO.sub.2                                                                   0.08                                                                  R/SiO.sub.2                                                                           0.31                                                                  H.sub.2 O/SiO.sub.2                                                                   18.95                                                                 Na.sup.+ /SiO.sub.2                                                                   0.12                                                           ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (7.541 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to contain somemordenite and a dense phase impurity, as shown in Table 10.

A portion of the as-synthesized product of this example was calcined at538° C. for 10 hours. Table 11 shows the X-ray diffraction pattern ofthis calcined mordenite-containing material.

                  TABLE 10                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        13.56           6.52     11.52                                                10.24           8.64     6.29                                                 9.06            9.76     18.68                                                6.57            13.48    16.32                                                5.78            15.32    7.94                                                 4.52            19.62    13.39                                                4.28            20.74    34.87                                                4.09            21.72    100.00                                               3.99            22.30    36.21                                                3.83            23.22    10.45                                                3.76            23.68    6.73                                                 3.46            25.72    23.31                                                3.35            26.58    76.76                                                3.22            27.70    15.64                                                3.14            28.38    6.25                                                 2.89            30.98    8.73                                                 ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        13.60           6.50     10.47                                                10.19           8.68     8.12                                                 9.08            9.74     22.54                                                6.55            13.52    15.60                                                6.36            13.92    6.09                                                 5.79            15.30    6.52                                                 4.52            19.64    11.97                                                4.27            20.82    37.82                                                4.09            21.72    100.00                                               3.99            22.30    33.60                                                3.83            23.22    11.00                                                3.75            23.70    7.80                                                 3.46            25.72    22.54                                                3.35            26.60    83.44                                                3.22            27.70    16.83                                                3.14            28.40    6.68                                                 2.88            31.08    9.46                                                 ______________________________________                                    

These examples demonstrate the present invention of synthesizingmordenite-type material from the required reaction mixture having a lowalkalinity, low YO₂ /X₂ O₃ molar ratio and directing agent of1,8-diamino-p-menthane. When the YO₂ /X₂ O₃ ratio in the reactionmixture is greater than about 70, a zeolite other than mordenite orother material composition begins to form. Synthesis conditions using aYO₂ /X₂ O₃, e.g. SiO₂ /Al₂ O₃, ratio at about 103 at low temperature(145° C.) for 1 week gave ZSM-5. Raising the temperature to 175° C. for3 days at this YO₂ /X₂ O₃, e.g. SiO₂ /Al₂ O₃, ratio gave mostly athermally unstable layered structure. Extending the crystallization timeto 5 days at 175° C. gave some mordenite and a dense phase productmixture. Synthesis conditions using YO₂ /X₂ O₃, e.g. SiO₂ /Al₂ O₃, rationear 21 either at low temperature (145° C.) for 1 week or highertemperature (175° C.) for 3 days gave high-silica mordenite. Lower R/YO₂ratio (0.16) at this YO₂ /X₂ O₃, e.g. SiO₂ Al₂ O₃, ratio gave a mixtureof mordenite and ZSM-5 at 145° C. for 1 week. These same ingredientratios at 95° C. for 1 week gave only an amorphous product.

Changes and modifications in the specifically described embodiments canbe carried out without departing from the scope of the invention whichis intended to be limited only by the scope of the appended claims.

What is claimed is:
 1. A method for synthesizing crystalline materialexhibiting a characteristic X-ray diffraction pattern includingd-spacing maxima values shown in Table 1 which comprises (i) preparing amixture capable of forming said material, said mixture comprisingsources of alkali or alkaline earth metal (M), an oxide of trivalentelement (X), an oxide of tetravalent element (Y), water and directingagent (R) of 1,8-diamino-p-menthane, and having a composition, in termsof mole ratios, within the following ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                         1      to 70                                              H.sub.2 O/YO.sub.2  10     to 100                                             OH.sup.- /YO.sub.2  0      to 0.25                                            M/YO.sub.2          0      to 2.0                                             R/YO.sub.2          0.10   to 2.0                                             ______________________________________                                    

(ii) maintaining said mixture under sufficient conditions including atemperature of from about 100° to about 200° C. until crystals of saidmaterial are formed; and (iii) recovering said crystalline material fromstep (ii), said recovered crystalline material containing said R.
 2. Themethod of claim 1 wherein said mixture has the following compositionranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                   10 to         30                                                H.sub.2 O/YO.sub.2                                                                          15 to         50                                                OH.sup.- /YO.sub.2                                                                          0 to          0.1                                               M/YO.sub.2    0.10 to       1.0                                               R/YO.sub.2    0.16 to       1.0.                                              ______________________________________                                    


3. The method of claim 1 wherein said mixture further comprises seedcrystals in sufficient amount to enhance synthesis of said crystallinematerial.
 4. The method of claim 3 wherein said seed crystals have thestructure of mordenite.
 5. The method of claim 1 wherein said X isaluminum, boron, iron, gallium, indium or a mixture thereof, and said Yis silicon, germanium, tin or a mixture thereof.
 6. The method of claim1 wherein X comprises aluminum and Y comprises silicon.
 7. A mixturecapable of forming crystals of mordenite structure upon crystallization,said mixture comprising sources of alkali or alkaline earth metal (M),trivalent element (X) oxide selected from the group consisting of oxideof aluminum, boron, iron, gallium, indium and mixtures thereof;tetravalent element (Y) oxide selected from the group consisting ofoxide of silicon, germanium, tin and mixtures thereof; water anddirecting agent (R) of 1,8-diamino-p-menthane, and having a composition,in terms of mole ratios, within the following ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                   1 to          70                                                H.sub.2 O/YO.sub.2                                                                          10 to         100                                               OH.sup.- /YO.sub.2                                                                          0 to          0.25                                              M/YO.sub.2    0 to          2.0                                               R/YO.sub.2    0.10 to       2.0.                                              ______________________________________                                    


8. The method of claim 1 comprising replacing ions of the crystallinematerial recovered in step (iii), at least in part, by ion exchange withan ion or a mixture of ions selected from the group consisting ofhydrogen and hydrogen precursors, rare earth metals and metals fromGroups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII of the PeriodicTable of Elements.
 9. The method of claim 2 comprising replacing ions ofthe crystalline material recovered in step (iii), at least in part, byion exchange with an ion or a mixture of ions selected from the groupconsisting of hydrogen and hydrogen precursors, rare earth metals andmetals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII ofthe Periodic Table of Elements.
 10. The method of claim 8 wherein saidreplacing ion is hydrogen or a hydrogen precursor.
 11. The method ofclaim 9 wherein said replacing ion is hydrogen or a hydrogen precursor.12. The recovered crystalline material of claim
 1. 13. The recoveredcrystalline material of claim
 2. 14. The R-containing productcrystalline material of claim
 8. 15. The R-containing productcrystalline material of claim
 9. 16. The R-containing productcrystalline material of claim
 10. 17. The R-containing productcrystalline material of claim 11.